Catalytic reforming



Nov. 30, 1943. A. BQWEL'VrY, JR., ETAL 2,3355717 CATALYT I C REFORMING Filed March 2a. 1940 MiO JJM. |WIN.

NUL mi kukxwl l Patented Nov. 3d, 1943 lUNlrletD STAT-Es PATENT oFFlcE.

cA'rALmc nEFoaMING Albert B. Welty. -Jr., Elizabeth, and Stephen F.

Perry, Roselle, N. J., assignors, by mesne assignments, to Standard Catalytic Company, a corporation of Delaware Application March as, i940, serial No. 326,418 3 claims. (c1. 19asoi This invention relates to catalytic' reforming in the presence of hydrogen and is more particularly concerned with certain improvements in the method of conducting the process by mweans of which the netquantity of free hydrogenpror duced therein may be regulated.

In our co-pending application, U. S. Serial Number 271,672, led May 4, 1939, now U. S; Patent 2,288,336 we have describedl a method of controlling the net quantity of hydrogen produced in a process o'f catalytic reforming in the presence of hydrogen which consists in increasing or decreasing the proportion of lower boiling hydrocarbons in the feed stock to effect an increase or a decrease respectively in the net quantity of tion or deposition thereon during vthe reaction hydrogen produced. The present application is f concerned with `another method of controlling 1 the net quantity of hydrogen produced in such hydrogenated o r otherwise chemically vrecon-v structed product, for example, of anti-knock `characteristics superior to those of the starting material, with or Without an accompanying change of Volatility and with or without an accompanying change in molecular weight. By the term "chemically reconstructed is meant something more than the mere removal of impurities or ordinary finishing treatments. The 'term catalytic reforming shallV be understood to include reactions such as dehydrogenation, aromatization vor cyclization, desulfurization, alkylation portion of a cycle of carbonaceous contaminants and sulfur. These contaminants are ordinarily of the type which can be removed by burning and hence the regeneration portion of the cycle consists in passing inert gases containing regulated quantities of oxygen or air through the catalyst massat a temperature which will initiate,

combustion of the contaminants and continuing the flow of such gases until substantially all combustible matter has been burned oif of the catalyst.

One of the principal advantages of conducting the catalytic reforming process in the presence of hydrogen is that the rate at which carbona` ceous contaminants are deposited on `the catalyst k is greatly retarded and hence the activity of the catalyst ismaintained for longer periods before t regeneration is necessary. The length of the reaction portion of the cycles may therefore be appreciably longer in catalytic reforming in the presence of hydrogen than in catalytic reforming reaction portion of said cycle, or more kfree hy-` drogen in the system than at the start of the re- Thus it is pOSsible and isomerization, all or some of which may occur to a greater or lesser extent during the process..

The term catalytic reforming in the presence -oi hydrogen" wherever used in the specification and claims shall be understood to mean a process of catalytic reforming which is carriedout under such conditions that there is either no overall net consumption of free hydrogen or there is an over- -all net production of free hydrogen therein.

Processes of catalytic reforming are characterin the absence of hydrogen. Y

The reaction portion of a cycle in catalytic reforming in the presence of hydrogen may, in the drogen. Wherever the terms "over-all net conl sumption of free hydrogen and overall net production of free hydrogen are used, they shall be understood to mean'that at theend of the reaction portion of a cycle there is at least 'as much free hydrogen in the system as at the start of the action portion of said cycle. that at any given instant there may be a net consumption of free hydrogen due to some disturbance in the operating conditions, but so long as there has been no net consumption of free hydrogen over the whole reaction portion of the cycle, the process comes within the above stated dennition of catalytic reforming in the presence .of hydrogen.

' We have now found that-the source from which the feed stock is obtained has an important bearing upon the net quantity of free hydrogen which is produced in catalytic reforming in the presence of hydrogen. For example, we have found that under certain Voperating conditions there will 600 cubic feet per barrel of oil from an East Texas heavy virgin naphtha, whereas under the same conditions only 400 cubic feet of hydrogen per barrel' of oil will be produced from a West Texas heavy virgin naphtha. We have also found that under the same conditions of temperature, pressure, and feed rate and in the presence of the same catalyst, there is a substantially greater net production of free hydrogen from a feed stock rich in parafnic' or naphthenic hydrocarbons, such as a virgin stock than there'is from a feed stock rich in oleiinic, aromatic or unsaturated hydrocarbons, such as a cracked stock. To illustrate this, two naphthas A and B are subjected to catalytic reforming in the presence of hydrogen. Naphtha A is a high sulfur debutanizer bottoms obtained from a cracked stock and naphtha B is a debutanized light East Texas virgin naphtha. These stocks, are subjected to treatment under the following conditions:

It will be noted that for the first six hours of the reaction portion of the cycle, 780 cubicl feet of hydrogen are produced per barrel of oil from' naphtha B, whereas only 180 cubic feet are produced from naphtha A. The temperature in the treatment of naphtha B is somewhat lower than that used in the treatment of naphtha A because kthe lower temperature is preferable for the treatment of naphtha B. However, as temperature is increased, the production of free hydrogen may also increase, particularly in the earlier hours of the reaction portion of a. cycle, so that if the temperature in the treatment of naphtha B had been as high as that usedin the treatment of naphtha A an even greater quantity of hydrogen may have been produced from the treatment of na htha B.

It is known that lower pressure an temperature both favor the net production of free hydrogem On the other hand, low pressure also favors the formation of coke and high temhigher `he a net production of free hydrogen of about desired net production of free hydrogen at all times throughout the reaction portion of a cycle.

The net production of free hydrogen tends to decrease as the reaction portion of the cycle proceeds and as the catalyst loses its activity in promoting the reforming reactions. Hence, according to one modification of the invention, a feed stock relatively rich in cracked or unsaturated hydrocarbons may be used in the early hours of the reaction portion of the cycle and then as the net production of' free hydrogen decreases the proportion of unsaturated hydrocarbons in the feed stock may be progressively decreased by the addition of saturated hydrocarbons. In this way,

the [net production of lfree hydrogen may be maintained.

According to another modification of the present invention, two different feed stocks, one rich in cracked material and the otherrich in virgin material, may be. subjected to treatment in two separate reaction vessels under conditions best adapted for the respective fractions, with'a common recycle gas recovery system for the two reactors. In this way, there will be a substantial net production of free hydrogen from the reactor-in which the virgin stock is being treated and a relatively small net production of free hydrogen or even a net consumption of free hydrogen`in the reactor in which the cracked stock is beingA treated. However, because of the fact that there is a common recyclegas recovery system, an overall net production of vfree hydrogen may be maintained even in the event that there is anet consumption of free hydrogen in the reactor in which the cracked stock is treated.

According to still another modification of the invention in. which the initial feed stock contains a substantial proportion of unsaturated hydrocarbons, the reaction portion of a cycle may be continued for a period of 6 to .15 hours or more or until the net production of free hydrogen is very small and then instead of discontinuing the reaction, a feed stock rich in saturated hydrocarbons. may beA substituted forV the initial feed perature causes excessive volatility and loss of yield of the valuable high octane number product. It is therefore desirable to operate the process of catalytic reforming in the presence of hydrogen at as high a pressure and at as low a temperature as may be consistent with the requirements of the process and the production of the maximum yieldl of high quality product.

The'present invention is directed to a method by which the net quantity of free hydrogen produced in catalytic reforming in the presence of .hydrogen may be regulated so that it'may be stock with the result that the reaction -portion oi' the cycle may be continued for several hours more before the lack of a net production of free hydrogen necessitates stopping the flow of oil and regenerating the catalyst.

The method of carrying out the improved process will be fully understood from the following means 9. Hydrogen or a gas rich in free hydrosition of the feed stock is initially selected and thereafter adjusted so that there will be the proper ratio of virgin to cracked material or saturated to unsaturated hydrocarbons to cause the gen is supplied to line l through line Il by means of pump I2.

The mixture of feed stock and gas rich in hydrogen is heated in heating means 9 to a temperature which will be suitable to maintain the required temperature in the reaction zone. The feed stock and gas rich in hydrogen mayA be heated together in the same heating means, in the manner illustrated in the drawing, or they may be heated separatelyin different heating means and thereafter combined. From heating means l the mixture of feed stock and hydrogen ows through line I3 into a reaction vessel I4 which contains a suitable catalyst I5 the nature of which will be more fully disclosed below. The

reacting materials may now through the reaction vessel in either an upward or downward direction.

Reaction vessel- I4 is maintained at a temperature between 800 and 105p F., preferably be- ,tween' 850 and 1000 F. and under a pressure between slightly above atmospheric and about 750 pounds per square inch. Suitable pressures in most cases are between 50 and 600 pounds per square inch although higher pressures can,1f course, be used. The rate at which the feed stock is passed through the reaction vessel may be between 0.3 and 5.0 volumes of liquid oil per volume of catalyst per hour and the quantity of gas rich in free hydrogen which accompanies the oil through the reaction vessel may be between 1000 and 10,000 cubic feet per barrel ofoil.

The products of reaction leave reaction vessel I4 through line I6, pass through a cooling means I1 and then discharge into a separating means I8 wherein liquid and gaseous products may be separated. The gaseous products which are rich in free hydrogen are removed from separating means ,I8 through lin-e I9 by means of pump 20 and returned to hydrogen supply tank I0 or recycled directly'to the system through line 2I. In the event it is necessary or desirable to scrub the recycle gases to remove a portion of the hydrocarbon constituents therefrom they ymay be passed through line 22 and scrubbing means 23 and then returnedto line I9 throughy line 24. If

too much gas is being produced or if it is desired for any other reason to remove a portion of it from the system it may be vented through line 25.

Returning to the separating means I8, the liquidproducts are removed therefrom through line 26 and introduced into a fractionating means 21 from which fractions too low boiling for the desired product are removed through line 28, fractions too high boiling for the desired product are removed through line 29, and fractions boiling in the rangeof the desired product are removed.

through line 30 and collected in tank 3i.

In the event it is desired to operate two separate reaction vessels with a common recycle gas recovery system the drawing illustrates how this may be done. In the drawing, similar pieces of apparatus are designated by the same number but the second unit is designated by numbers marked prime For example, the reaction vessel of the 'second' unit is I4', the heating means is 9', the separating means is IB and vso on.V Certain pieces of equipment such as the feed level which the particular catalyst used is known supply tanks I, 2 and 3, and the-fractionating means 21 need not be duplicated, one item serving both units. In some cases it may be desirable to use separate fractionating means for each reaction `zone in order to'keep the liquid products of eachxzone separate, and in such cases a comman recycle gas system may of course be used.

It will be understood also that more than two units may be operated with a common recycle gas recovery system, the essential purpose being to combine units operating on different feed stocks sov that there will be an overall net production of free hydrogen even though one or more units may show a net consumption of free hydrogen.

. The flow of oil and hydrogen through the rekaction vessels is continued until 1) there ceases things occurs ilrst. In most cases the second of these things will occur rst, after from 0.25 to 50 hours or more, depending upon the feed rate and temperature. The shorter period lengths will be used at the higher feed rates and temperatures.y 'The flow of oilcand hydrogen is then stopped and the catalyst is subjected to any suitablregeneration treatment. One convenient method is to pass hot inert gases containing regulated quantities of oxygen through the catalyst mass until substantially all combustible material has been burned off. Following the regeneration treatment, the flow of oil and hydrogen may be resumed. y

The catalysts used in the process may be selected from a wide variety of different materials which promote reforming. Among these may be mentioned oxides or suldes of metals of the II, IV, V, VI and VIII groups of the periodic system, especially molybdenum, tungsten, chromium, vanadium, cobalt and nickel. These materials are preferably used in combination with supporting materials such as natural or activated clays, synthetic clays, bauxite, alumina, acti-- vated alumina, alumina gel, peptized alumina, silica, silica gel, aluminum silicates of various types, silica-magnesia, and many others. The catalyst compositions can be prepared in diii'erent ways as by mechanical mixing, impregnation and co-precipitation. -They' are preferably used in the form .of small lumps, cubes, pills, tablets, pellets, granules or other pieces of regular or ir regular shape and of relatively small dimension.

The feed stocks to which the present` process may be applied should consist of hydrocarbons substantially boiling in the gasoline range, say from about to 450 F. or somewhat higher. Subject'to the predominantly saturated or unsaturated ,character of the feed stock that may' be required in each particular case, the feed \stocls may be derived from any souice. For exsuch as tetraethyl lead and iron carbonyl, or may be blended with agents such as iso-pentane, alkylated isobutaneor otherv iso-paraflins, isopropyl ether and hydrogenated polymers of isobutylene. Suitable oxidation and gum inhibiting agents may also be'added,-

This invention is not limited by any theories of the mechanism .of'the reactions nor by any details which have been given merely for purposes of illustration, but is limited only in and by the following claims in which it is intended to claim all novelty inherent inthe invention.

We claim:

1. In a, process ofv catalytic reforming in the presence ,of hydrogen and in the presence of a catalyst comprising' aluminum oxide and a compound of a metal of the VI group of the periodic system, the method of maintaining a substantially constant net production of free hydrogen during a reaction portion of the cycle which comprises progressively increasing the Vproportion of saturated hydrocarbons in the feed stock as the reaction .portion of the cycle proceeds.

2. In a process of catalytic reforming in the presence of hydrogen and in the presence of a" catalyst comprising aluminum oxide and an oxide of a metal o: the VI group of the periodic system and in' which a reaction portion of the cycle is continued until the net quantity of free hydrogen being produced is insumcient to maintain the required concentration of hydrogen in the recycle gases, the method ot prolonging the reaction portion of the cycle which comprises increasing the proportion of saturated hydrocarbons in the feed stock `when it is observed that the net quantity of free hydrogen produced falls below the level necessary to maintain the required concentration of hydrogen'in the recycle gases 3., In the catalytic reforming of a hydrocarbon oil containing both saturated and unsaturated hydrocarbons in the presence oi' hydrogen and in the presence of a catalyst comprising an oxide of a metal ofthe VI group ot the periodic system, the improved method of operation which consists in separating the hydrocarbon oil into two tractions. one rich in the saturated constituents thereof and the other rich in the unsaturated constituents, subjecting the fraction rich in the unsaturated constituents to reforming in the early stages of the reaction portion of the cycle and subjecting the fraction rich in the saturated constituents to reforming in the later stages of the same reaction portion of the same cycle.

ALBERT B. WELTY, JR. STEPHEN F. PERRY. l 

